JP5165866B2 - Method and apparatus for supplying electron donor to microorganism and bioreactor using the same - Google Patents

Description

  The present invention relates to a method and apparatus for supplying an electron donor to a microorganism, and a bioreactor using the same. More specifically, the present invention relates to a microorganism for efficiently removing substances present in a liquid to be treated, for example, nitrogen compounds such as ammonia, nitrate ions, and nitrite ions, by biological treatment using microorganisms. The present invention relates to an electron donor supply method and apparatus, and a bioreactor using the same.

  When performing biological treatment using microorganisms, it is sometimes necessary to supply an organic substance such as alcohol as an electron donor that serves as an energy source for microorganisms. For example, in a sewage treatment process in which nitrogen compounds such as ammonia present in the liquid to be treated are removed by biological treatment, methanol is used to accelerate the denitrification reaction during the denitrification reaction after the nitrification reaction. A necessary amount is supplied by a pump device controlled by a control device as an electron donor serving as an energy source for microorganisms (Patent Document 1).

  In addition, the liquid to be treated is brought into contact with one surface of a sheet-like polymer gel on which microorganisms effective for removing nitrogen compounds such as ammonia existing in the liquid to be treated and the other surface is necessary for the denitrification treatment. In a nitrogen removal bioreactor (Patent Documents 2 and 3) in which an electron donor as an energy source is contacted, alcohol serving as an energy source of microorganisms is supplied as an electron donor. Alcohol is supplied by operating a circulation pump, various valves, and instruments using a circulation path that connects the space inside the polymer gel carrier formed in the bioreactor and the alcohol storage tank with piping. The alcohol supply timing and amount are controlled.

  Here, if the supply of alcohol is excessive, microorganisms may not be consumed and alcohol may remain in the water and deteriorate the water quality. On the other hand, if the supply amount of alcohol is small, the energy source will be insufficient. As a result, the denitrification reaction becomes insufficient and the concentration of nitrous acid increases. Therefore, the supply of alcohol is controlled such that the supply amount and timing are controlled using a pump or the like, and alcohol diluted to a concentration of about 10% by volume is supplied from the alcohol storage tank.

Japanese Patent No. 3260554 Japanese Patent No. 3340356 Japanese Patent No. 2887737

  Therefore, an electron donor supply method to microorganisms in a conventional bioreactor is a pump or control for maintaining a constant supply amount of an alcohol solution such as methanol or ethanol, which is an electron donor serving as an energy source for denitrifying bacteria. A series of facilities such as an apparatus is required, and the facility becomes large and the operation of the facility becomes complicated. Therefore, there is a problem that the running cost becomes high.

  Also, if the alcohol solution such as methanol or ethanol is in high concentration, the microorganism may die if the solution is brought into direct contact with the microorganism, and the solution must be diluted with water so that the microorganism does not die. It also has the hassle of having to do it. Moreover, since the alcohol undiluted solution cannot be used, it must be diluted and stored, and there is a problem that the storage tank is enlarged accordingly. Furthermore, the conventional electron donor supply method for microorganisms has a problem that waste alcohol having a large amount of impurities cannot be used because the diluted alcohol is directly supplied to the microorganisms. For example, waste alcohol generated in the tea refining process contains catechins. Therefore, when this is used as an energy source, there is a risk that microorganisms will be killed even if diluted. Therefore, since it must be used in a state in which impurities are removed, waste alcohol cannot be reused in practice.

  Furthermore, an electron donor as an energy source necessary for denitrifying bacteria is brought into contact with a space surrounded by a sheet-like polymer gel on which microorganisms are immobilized as described in Patent Document 2 or 3. In the type of nitrogen removal bioreactor, the amount of alcohol that does not overflow from the reactor must be supplied into the reactor through the supply pipe, so that the larger the reactor, the better the alcohol can be diffused to every corner. It becomes difficult, and enlargement is difficult. Also, with such an alcohol supply method, it is difficult to reduce the thickness of the apparatus.

  Then, an object of this invention is to provide the electron donor supply method and apparatus to microorganisms which can supply an electron donor to every corner and the reactor can be enlarged or reduced in thickness. Another object of the present invention is to provide a method and apparatus that can easily supply an electron donor to a microorganism without using a pump or a control device. Another object of the present invention is to provide a method and apparatus for supplying an electron donor to a reusable microorganism using waste alcohol as an energy source.

  Another object of the present invention is to provide a compact bioreactor that does not require management, with respect to the supply of electron donors to microorganisms. Furthermore, an object of the present invention is to provide a bioreactor for efficiently removing harmful substances such as ammonia, nitrate ions and nitrite ions present in the liquid to be treated.

  A device for supplying an electron donor to a microorganism of the present invention for solving such a problem is a volatile organic substance functioning as an electron donor that serves as an energy source for the microorganism (hereinafter also referred to simply as a volatile organic substance). And a liquid permeable member capable of permeating volatile organic matter, and a container having a sealed structure having at least a part of a non-porous membrane, and the liquid permeable member is accommodated in the container together with the volatile organic matter. The non-porous membrane portion of the container supplies the microorganisms around the container at a speed controlled by the molecular permeation performance of the non-porous film. In addition, the electron donor supply method for microorganisms of the present invention is a volatile organic substance functioning as an electron donor serving as an energy source for microorganisms in a sealed container having at least a part of a non-porous membrane. A liquid penetrating member capable of penetrating organic matter is accommodated, volatile organic matter penetrating the entire surface of the liquid penetrating member is supplied to every corner of the nonporous membrane, and volatile organic matter is removed from the nonporous membrane portion of the container. The microorganisms around the container are supplied at a speed governed by the molecular permeation performance of the porous membrane.

  In addition, an electron donor supply apparatus for a microorganism of the present invention for solving such a problem includes a liquid penetrating member capable of penetrating a volatile organic substance functioning as an electron donor serving as an energy source for the microorganism, and a non-porous material. It includes a sealed container with a membrane in part and a supply port that can be replenished with volatile organic matter provided in the container. By replenishing the volatile organic matter from the supply port, the liquid permeable material is permeated into the liquid penetrating member. The volatile organic substance is supplied from the non-porous membrane portion of the container to the microorganisms around the container at a speed governed by the molecular permeation performance of the non-porous film. In addition, the method for supplying an electron donor to a microorganism according to the present invention allows a volatile organic substance functioning as an electron donor serving as an energy source for the microorganism to penetrate into a sealed container having at least a part of a non-porous membrane. A supply port capable of containing the liquid penetrating member that can be replenished and replenishing the volatile organic matter is provided in the container, and the liquid penetrating member is permeated into the liquid penetrating member by replenishing the volatile organic matter from the supply port. The volatile organic matter penetrating the entire surface is supplied to every corner of the non-porous membrane, and the volatile organic matter is transferred from the non-porous membrane portion of the vessel to the periphery of the vessel at a speed controlled by the molecular permeation performance of the non-porous membrane. Supply to microorganisms.

  Since the volatile organic matter uniformly permeates into every corner of the liquid penetrating member contained in the container by capillary action, the volatile organic matter is spread to every corner of the surface of the non-porous membrane in contact with the liquid penetrating member. Can be supplied. Therefore, the volatile organic substance can be uniformly and gradually released from the entire surface of the non-porous membrane in contact with the liquid penetrating member.

  The liquid penetrating member housed in the container holds the liquid and functions as a liquid passage. It also serves as a spacer. Therefore, even when a part or the whole of the container is crushed due to a pressing force, a volatile organic matter permeation path is secured, and the volatile organic matter penetrates to every corner of the liquid permeable member. Does not reduce the sustained release area.

  Volatile organic matter penetrating the liquid penetrating member is released slowly at a moderate rate governed by the molecular permeation performance of the non-porous membrane, so the concentration does not affect the survival of microorganisms around the container. It is supplied as an electron donor to the microorganism in a diluted state. In addition, since the permeation rate of volatile organic matter is governed by the molecular permeation performance of the non-porous membrane, the amount required by microorganisms can be adjusted by adjusting this molecular permeation performance with the membrane material, film thickness, membrane density, etc. The electron donor can always be supplied slowly.

  In addition, by providing a supply port that can replenish volatile organic matter, it is possible to replenish the reduced amount of volatile organic matter in the container, so that the amount of electron donor required by the microorganism can be supplied over a long period of time. It becomes possible to supply slowly.

  Here, although the container of the electron donor supply device of the present invention is not limited to a specific shape, it is formed into a bag shape with only a non-porous film and contains a liquid penetrating member and a volatile organic substance. It is preferable. By making the container into a bag shape, it becomes a very easy-to-use form, and when the volatile organic matter in the container is exhausted and it becomes impossible to supply volatile organic matter to the microorganisms around the container, the liquid penetrating member and volatile By simply replacing the organic matter with a new sealed bag, the supply of volatile organic matter to the microorganisms can be controlled again. Moreover, it is preferable to accommodate the liquid penetrating member so as to be disposed throughout the interior of the bag. By accommodating the liquid penetrating member in this way, volatile organic substances can be uniformly released from the entire surface of the non-porous membrane. In other words, the sustained release surface of the volatile organic substance with respect to the size of the container can be maximized.

  Further, as described above, it is preferable that the container is provided with a supply port for replenishing volatile organic substances, or the container is connected to a volatile organic substance storage tank so that the volatile organic substances can be replenished as necessary. It is preferable to provide. In this case, if the stock solution of the volatile organic substance is stored in the tank, the volatile organic substance is transferred to the tank and the container when the volatile organic substance penetrating the liquid penetrating member contained in the bag is reduced. It can be replenished by the pressure difference.

  Here, when a pressing force is applied to the lower portion of the container, the surplus volatile organic matter that has not permeated the liquid penetrating member moves to and is stored in the upper portion of the container where the pressing force is not applied. In this case, in the lower part of the container to which the pressing force is applied, a penetration path for the volatile organic substance is secured and the volatile organic substance penetrates to every corner of the liquid penetrating member, and the container is crushed and thinned by the pressing force. In addition, volatile organic substances are stored in the upper part of the container where no pressing force is applied. Therefore, the stored volatile organic matter is supplied by the reduced amount of the volatile organic matter penetrating the liquid penetrating member, and the volatile organic matter is uniformly and gradually released from the non-porous membrane portion at the bottom of the container. Can do.

  Such a form can also be obtained by processing the container in advance. For example, the container is divided into two regions and a liquid penetrating member is disposed across the two regions so that the two regions communicate with each other, and the volatile organic substance is stored in one of the two regions. Good.

  In addition, the electron donor supply apparatus for microorganisms of the present invention includes a liquid permeable member capable of permeating volatile organic substances and a non-porous film, and the liquid permeable member is sandwiched between two non-porous films. While the laminated body is formed, the peripheral part of the laminated body is heat-sealed, and the capillary structure of the liquid permeation member is closed. An electron donor supply device for a microorganism having such a structure includes a step of forming a laminate by sandwiching a liquid permeation member capable of permeating volatile organic substances with a non-porous film, and heat-sealing the peripheral portion of the laminate And a step of closing the capillary structure of the liquid penetrating member. Further, any one of a step of forming a laminate by sandwiching a liquid permeation member capable of permeating volatile organic substances with a non-porous film, and a carrier capable of supporting microorganisms and a protective material for protecting the laminate from an external impact. It can be obtained by a production method including a step of providing either or both on the surface of the laminate, and a step of heat-sealing the peripheral portion of the laminate to close the capillary structure of the liquid permeation member.

  Therefore, the capillary structure of the liquid penetrating member is blocked at the peripheral edge of the heat-sealed laminate. Further, since the liquid permeation member and the non-porous film are welded at the peripheral edge of the laminate, the region where the volatile organic matter permeates is sealed. In this case, since the sealed region into which the volatile organic substance permeates can be formed only by heat-sealing the peripheral edge of the laminate, its production is very easy. In addition, even when one or both of a carrier capable of supporting microorganisms on the surface of the non-porous membrane and a protective material that protects the laminate from external impacts are provided, the peripheral portion of the laminate is supported by the carrier or By heat-sealing together with the protective material, a multilayer structure can be easily formed.

  Here, as the volatile organic substance in the present invention, methanol, ethanol, propanol, benzene, toluene, phenol and the like are appropriately used, but waste alcohol can also be used. The non-porous membrane has a role like “molecular sieve”, and as the molecular weight of the molecule to be permeated increases, it becomes difficult to permeate the molecule. Therefore, even if antibacterial molecules that are toxic to microorganisms, such as impurities such as catechins and cyanide compounds, are mixed in volatile organic substances, catechins with large molecular weights and cyanogen compounds with large polarities are difficult to permeate. It becomes possible to permeate volatile organic substances that are harmless to microorganisms as a main component.

  In addition, in the electron donor supply apparatus for microorganisms according to the present invention, as the non-porous film, for example, in addition to plastic films such as polyethylene, polypropylene, polyester, nylon, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, and vinylon, Gas-liquid membranes such as polyethylene, ethylene acrylic acid copolymer, and polyethylene terephthalate mixture can be used, but use of polyethylene and polypropylene, which are inexpensive and excellent in durability and chemical resistance, especially permeate molecules. Easy low density polyethylene is preferred. Of course, it is not limited to these materials.

  The method and apparatus for supplying an electron donor to a microorganism of the present invention can be used for any facility that needs to supply an electron donor to a microorganism and for all bioreactors. For example, a bioreactor in which a carrier on which microorganisms effective for removing a target component are immobilized is arranged around a non-porous membrane portion of an electron donor supply apparatus can be configured. In addition, a bioreactor can be configured in which the electron donor supply device of the present invention is applied to a carrier with the non-porous membrane portion applied thereto. It is also possible to configure a bioreactor in which the carrier is shaped like a bag and the above-described electron donor supply device for microorganisms is accommodated in the space inside the bag.

  In this case, the volatile organic matter that has permeated the liquid penetrating member permeates the non-porous membrane and is gradually released around the container. Therefore, the volatile organic matter is released directly into the carrier on which the microorganism is fixed or once into the carrier bag. Supplied as an electron donor. Therefore, it becomes possible to supply the volatile organic substance functioning as an electron donor, which is an energy source of the microorganism, to the microorganism fixed to the bioreactor autonomously with a uniform and gentle sustained release property.

  Furthermore, the bioreactor of the present invention is formed by directly supporting microorganisms on the surface of the non-porous membrane of the container of the electron donor supply apparatus for microorganisms described above. In this case, since the microorganism is fixed on the surface through which the volatile organic substance permeates, almost the entire amount of the supplied volatile organic substance is directly supplied to the microorganism. Here, the fixation of the microorganism is performed by making the surface of the membrane having a nonporous membrane hydrophilic, thereby facilitating the adhesion of the polymer gel to the surface, or by raising the surface of the nonporous membrane. Microbes are attached directly to the surface.

  In the bioreactor of the present invention, the carrier is a water-absorbing polymer. By using the water-absorbing polymer, the water holding power and water absorbing power of the carrier are enhanced, so that it becomes possible to efficiently remove the target component while supporting the microorganisms in a good state.

  Furthermore, the bioreactor according to the present invention includes one or two microorganisms that oxidize or reduce the microorganisms effective for removing the target component in the liquid to be treated on the carrier on which the microorganisms can be fixed and the substances produced by the microorganisms. The liquid to be treated is brought into contact with one surface of the carrier on which the seeds or more are immobilized, and the above-mentioned electron donor supply device is brought into contact with the other surface. As an example of a microorganism, an ammonia-oxidizing bacterium is an effective microorganism for removing a target component, and a denitrifying bacterium is a microorganism that reduces substances produced by an effective microorganism for removing a target component. Furthermore, by using nitrite-oxidizing bacteria as microorganisms that oxidize substances produced by microorganisms that are effective in removing the target components, nitrite ions can be oxidized to nitrate ions, and the processing efficiency is improved. Therefore, the nitrogen compound (ammonia, nitrate ion, nitrite ion) in the liquid to be treated can be converted into harmless nitrogen gas.

  Next, the method for removing gaseous ammonia of the present invention comprises a first step of bringing gaseous ammonia and water into contact with each other to dissolve the gaseous ammonia in water; Or a second step of contacting ammonia oxidizing bacteria, nitrite oxidizing bacteria, and denitrifying bacteria in a microbial area, and arranging the electron donor supply device of the present invention in the microbial area, Is supplied from the non-porous membrane part of the electron donor supply device to the denitrifying bacteria around the container at a rate governed by the molecular permeation performance of the non-porous membrane, and nitrite ions or ammonia produced by ammonia oxidizing bacteria Nitrite ions produced by oxidizing bacteria and nitrate ions produced by nitrite oxidizing bacteria are reduced to nitrogen gas. Further, the gaseous ammonia removing apparatus of the present invention includes a gas introduction part for introducing gaseous ammonia, watering means for obtaining water containing ammonia by bringing water into contact with the gaseous ammonia introduced from the gas introduction part, and ammonia A microbial treatment region for decomposing ammonium ions contained in ammonia-containing water by contacting the hydrated water, and ammonia oxidizer or ammonia oxidizer and nitrite oxidizer and denitrifier are present in the microbial treatment region In addition, the electron donor supply device of the present invention is arranged.

  Gaseous ammonia dissolves in water and becomes ammonium ions. Ammonium ions come into contact with ammonia-oxidizing bacteria and are oxidized to nitrite ions. If nitrite-oxidizing bacteria are also present, they are oxidized to nitrate ions. The nitrite ions produced by the ammonia oxidizing bacteria or the nitrite ions produced by the ammonia oxidizing bacteria and the nitrate ions produced by the nitrite oxidizing bacteria come into contact with the denitrifying bacteria and are reduced to nitrogen gas. Here, an electron donor is required for the denitrifying bacteria to function. Therefore, by disposing the electron donor supply device of the present invention in the microbial treatment region, the denitrifying bacteria can be functioned by slowly supplying volatile organic substances serving as electron donors to the denitrifying bacteria.

In addition, you may use the bioreactor of Claim 26 instead of a microorganism treatment area | region.

  According to the electron donor supply method and apparatus for microorganisms of the present invention, volatile organic substances uniformly permeate into the liquid penetrating member accommodated in the container by capillary action, so that the liquid penetrating member contacts the liquid penetrating member. Volatile organic matter can be supplied to every corner of the non-porous membrane surface. Therefore, volatile organic substances can be uniformly and gradually released from the entire surface of the non-porous membrane that is in contact with the liquid-permeable member, so that the volatile organic substances are uniformly distributed from the entire surface of the non-porous membrane even when the apparatus is enlarged. When the entire container is composed of a non-porous membrane and the liquid penetrating member is accommodated so as to occupy the entire area of the container, the volatile organic matter is gradually adjusted relative to the size of the container. You can maximize the surface.

  In addition, by infiltrating the volatile organic substance into the liquid permeable member, it is possible to prevent the container bottom from expanding due to the volatile organic substance accumulating at the bottom of the container and the container from expanding due to gasification of the volatile organic substance. It is also possible to reduce the thickness of the container. Accordingly, when a plurality of electron donor supply devices are collected and accommodated in a processing tank or the like, the accommodation density of the electron donor supply devices can be increased. In addition, since the liquid penetrating member also functions as a core material, the strength of the container of the electron donor supply device can be improved by housing the liquid penetrating member in the container.

  Further, the liquid penetrating member accommodated in the container holds the liquid and functions as a liquid passage. It also serves as a spacer. Therefore, even when a part or the whole of the container is crushed due to a pressing force, a volatile organic matter permeation path is secured, and the volatile organic matter penetrates to every corner of the liquid permeable member. It is possible to uniformly and gradually release volatile organic substances from the non-porous membrane part of the container even when used in an environment where pressing force is applied, for example, by immersing the container in water, without reducing the sustained release area. is there.

  Further, according to the method and apparatus for supplying an electron donor to a microorganism of the present invention, a non-porous volatile organic substance that functions as an electron donor serving as an energy source for the microorganism and a liquid penetrating member that can permeate the volatile organic substance are non-porous. By storing in a sealed container having a porous membrane in part, volatile organic substances can be gradually permeated from the non-porous membrane and slowly supplied to the microorganisms. Therefore, it is not necessary to provide a facility for maintaining the supply amount of the volatile organic substance at a constant amount, and the running cost can be greatly reduced.

  Furthermore, by providing a supply port that can replenish volatile organic matter, it becomes possible to replenish the reduced amount of volatile organic matter in the container, so that the amount of electron donor required by the microorganism can be supplied over a long period of time. It becomes possible to supply slowly.

  In addition, when a pressing force is applied to the lower part of the container, surplus volatile organic matter that has not permeated the liquid penetrating member moves to and is stored in the upper part of the container where the pressing force is not applied. In this case, in the lower part of the container to which the pressing force is applied, a volatile organic substance permeation path is secured and the volatile organic substance penetrates to every corner of the liquid penetrating member, and the container is crushed and thinned by the pressing force. In addition, volatile organic substances are stored in the upper part of the container where no pressing force is applied. Therefore, the stored volatile organic matter is supplied by the reduced amount of the volatile organic matter penetrating the liquid penetrating member, and the volatile organic matter is uniformly and gradually released from the non-porous membrane portion at the bottom of the container. Can do.

  Further, according to the electron donor supply method and apparatus of the present invention, even when the volatile organic substance is permeated into the liquid permeation member as a stock solution, the volatile organic substance molecules permeate the non-porous membrane little by little. On the other hand, volatile organic substances can be supplied slowly. Therefore, the process of diluting volatile organic substances with water to the extent that microorganisms do not die can be omitted, and labor can be saved, and volatile organic substances can be supplied with the same volume of liquid for a long time. It becomes. In addition, it is possible to prevent accidents in which the undiluted solution is accidentally supplied to kill microorganisms. Further, the container itself can be made smaller, and even when a storage tank for replenishing the volatile organic matter is present in the container, the tank capacity can be reduced because it can be stored in the undiluted stock solution state.

  In addition, since the non-porous membrane functions as a molecular sieve, it becomes difficult to permeate the molecule as the molecular weight of the molecule to be permeated increases. Therefore, even if antibacterial molecules that are toxic to microorganisms such as impurities such as catechin and cyanide are mixed in organic substances, catechins having a large molecular weight are difficult to permeate and volatile organic substances that are harmless to microorganisms are not present. Permeated as a main component and gradually released out of the container, and most of the impurities remain in the container. Accordingly, a volatile organic substance containing impurities such as waste alcohol can be used. The recycling of waste alcohol can reduce the amount of waste, which is favorable for the environment and can make the waste useful and reduce the cost of the energy source. For example, waste alcohol that is currently regenerated through processes such as distillation and purification can be used as is without performing these treatments, and a significant cost reduction can be realized. More specifically, waste alcohol produced in food and pharmaceutical manufacturing processes can be effectively used as an energy source for microorganisms without undergoing a removal process such as distillation of substances having microbial toxicity (such as catechins and cyanide compounds).

  Furthermore, in the electron donor supply method and apparatus of the present invention, a volatile organic substance and a liquid permeable member capable of penetrating the volatile organic substance are sealed in a bag-like container made of a non-porous film. Until the volatile organic matter is consumed, the volatile organic matter is supplied autonomously slowly and uniformly at a constant rate. Therefore, it is possible to simplify the apparatus configuration without requiring maintenance. Further, when the volatile organic matter in the container is exhausted, it is only necessary to replace the volatile organic substance with a new bag-like container sealed with a liquid penetrating member that can permeate the volatile organic substance. Used bag-shaped containers can be recycled by being recycled.

  Further, in the electron donor supply apparatus for microorganisms of the present invention, the peripheral portion of the laminate in which the liquid penetrating member is sandwiched between non-porous membranes is heat sealed, and the capillary structure of the liquid penetrating member is closed. When a volatile organic substance is supplied to the liquid penetrating member, the non-porous membrane sandwiching the liquid penetrating member and the capillary structure at the periphery of the liquid penetrating member are blocked, and the region where the volatile organic substance penetrates is sealed. In this state, the same function as a sealed container is exhibited. Therefore, the volatile organic substance can be gradually released uniformly from the entire surface of the non-porous film. In addition, the electron donor supply apparatus for microorganisms having such a structure includes a step of forming a laminate by sandwiching a liquid permeation member that can infiltrate volatile organic substances with a non-porous film, and a peripheral portion of the laminate. And a step of closing the capillary structure of the liquid permeation member by heat sealing. Alternatively, any one of a step of forming a laminated body by sandwiching a liquid permeable member capable of permeating volatile organic substances with a non-porous film, and a carrier capable of supporting microorganisms and a protective material for protecting the laminated body from external impact Or it is obtained by the manufacturing method including the process of providing both on the surface of a laminated body, and the process of heat-sealing the peripheral part of a laminated body and obstruct | occluding the capillary structure of a liquid permeable member. Therefore, it is possible to form a sealed region into which the volatile organic substance permeates only by heat-sealing the peripheral edge of the laminated body. Easy. In addition, even when one or both of a carrier capable of supporting microorganisms on the surface of the non-porous membrane and a protective material that protects the laminate from external impacts are provided, the peripheral portion of the laminate is supported by the carrier or By heat-sealing all the protective materials together, a multilayer structure can be easily formed. Therefore, if the multilayer structure is formed in a large area and thinly, a large and thin device can be easily manufactured.

  In addition, according to the bioreactor using the electron donor supply apparatus of the present invention, the volatile organic substance functioning as an electron donor to the microorganism is autonomously and uniformly and gradually released on a carrier on which the microorganism is fixed. Even if the bioreactor is enlarged, if the entire electron donor supply device is composed of a non-porous membrane, the liquid permeation member accommodated in the container is permeated. Volatile organic substances are uniformly permeated from the entire surface of the non-porous membrane and gradually released around the container. Therefore, the volatile organic substance is supplied to every corner of the surface on which the microorganisms requiring the electron donor are fixed. Moreover, the container containing the liquid permeable member infiltrated with the volatile organic substance is disposed near the carrier on which the microorganisms are fixed so as to supply autonomously with uniform and gentle sustained release. It can be handled independently and is convenient to use. In the case of a bioreactor in which microorganisms are directly supported on the surface of a non-porous membrane, the entire amount of supplied volatile organic substances is directly supplied to the microorganisms, so that they are consumed wastefully or contaminate the liquid to be treated. In addition, there is no need for a separate container with a carrier attached.

  Furthermore, the use of a water-absorbing polymer as a carrier in the bioreactor of the present invention increases the water retention capacity and water absorption capacity of the carrier, so that microorganisms can be supported in a good state and target components can be efficiently removed. It becomes possible.

  Further, according to the method and apparatus for removing gaseous ammonia of the present invention, since the electron donor supply apparatus of the present invention or the bioreactor using the electron donor supply apparatus of the present invention is used, It is not necessary to provide equipment for maintaining the supply amount of the volatile organic substance serving as the electron donor at a constant amount, and the running cost for removing gaseous ammonia can be greatly reduced. In addition, since the container of the electron donor supply device can be thinned, the electron donor supply devices can be integrated and arranged with high density. Therefore, it is possible to reduce the size and size of the gaseous ammonia removal device.

  Hereinafter, the configuration of the present invention will be described in detail based on embodiments shown in the drawings.

  As an embodiment of an electron donor supply apparatus for microorganisms according to the present invention, an electron donor supply apparatus of a type in which a liquid penetrating member is accommodated in a container will be described with reference to FIGS.

  An electron donor supply apparatus 1 shown in FIG. 1 includes at least a volatile organic substance 3 that functions as an electron donor serving as an energy source for microorganisms, a liquid penetrating member 13 that can permeate the volatile organic substance, and a non-porous film. A container 4 having a sealed structure provided in part, and a liquid penetrating member 13 is accommodated together with the volatile organic substance 3 in the container 4 so that the volatile organic substance 3 is nonporous from the portion of the nonporous membrane 2 of the container 4. This is supplied to microorganisms around the container 4 at a speed governed by the molecular permeability of the membrane 2. In the present embodiment, the container 4 is formed into a bag shape that is entirely composed of a non-porous membrane 2, and a sheet-like liquid infiltrating member 13 in which a volatile organic substance 3 is infiltrated by welding the periphery with a heat seal or the like. Is laminated with the non-porous film 2, but the form and structure are not particularly limited. For example, it is good also as a structure which seals a rod-shaped liquid permeable member with a volatile organic substance by making a container into a tube shape. Further, the bag-like container (sometimes simply referred to as a bag) 4 is not particularly limited to one that is entirely constituted by a non-porous film, and for example, only one side may be constituted by a non-porous film, A further part of the surface may be composed of a non-porous film. At this time, the other surface or the remaining portion may be formed of a film that does not transmit volatile organic substances. By comprising in this way, it is possible to release a volatile organic substance gradually from the desired part of a container.

  The volatile organic substance 3 that functions as an electron donor serving as an energy source for microorganisms is a substance that is not toxic to microorganisms and has the property of not corroding the non-porous film 2, and the non-porous film Those having molecular weight and properties capable of penetrating 2 are appropriately selected. Illustrative examples include methanol, ethanol, propanol and the like. In addition, although benzene, toluene, phenol, etc. can be utilized depending on microorganisms, it is not limited to these.

  Here, the volatile organic material 3 can be used as it is. Conventionally, when alcohol such as methanol or ethanol is used as an energy source for microorganisms, it has been necessary to dilute with water to such a concentration that the microorganisms do not die. Since it is slowly supplied to the microorganisms, the microorganisms will not die even if a volatile organic substance stock solution is used. Note that it is not always necessary to use a volatile organic substance stock solution. Even if the volatile organic substance stock solution is diluted with water or mixed with impurities, volatile organic molecules are not used. Slowly supplied to microorganisms through the porous membrane. Therefore, even if impurities such as catechins and cyanide compounds that are toxic to microorganisms are mixed with volatile organic substances, catechins with large molecular weights and cyanide compounds with large polarities are difficult to permeate. A harmless volatile organic substance can be permeated as a main component and can be gradually released out of the container, and impurities are almost left in the container. Accordingly, a volatile organic substance containing impurities such as waste alcohol can be used.

  The liquid penetrating member 13 that can permeate the volatile organic material 3 may be any member that can uniformly diffuse the volatile organic material 3 by capillary action. Illustrative examples include porous bodies, fibrous materials, and powders. More specifically, for example, a porous body may be a metal porous body, a ceramic porous body, a flexible plastic porous body, or the like. That is, if a member such as a highly rigid metal or ceramic is used, the container 4 is hardly deformed. If a flexible member is used, the container 4 can be made flexible and easily deformed. Examples of the fibrous material include paper such as filter paper, non-woven fabric, and other foams. Furthermore, any powder may be used as long as it fills the container 4 and can penetrate the volatile organic substance 3. In addition, polyethylene foam, polyurethane foam, vinyl chloride sponge, natural rubber sponge, silicon rubber sponge, cellulose sponge and the like can also be used. The liquid penetrating member 13 is not limited to the one exemplified here. Here, since the volatile organic substance 3 is supplied through the liquid permeable member 13, the liquid permeable member 13 can supply the volatile organic substance 3 to the entire sustained release surface constituted by the non-porous film 2 of the container 4. It is preferable to make it a size. In this case, the volatile organic substance 3 is supplied to the entire surface of the non-porous membrane 2 and permeates through the non-porous membrane 2 to be uniformly and gradually released. As shown in FIG. 1, the container 4 is formed into a bag shape composed entirely of a non-porous membrane 2, and a sheet-like liquid infiltration member 13 in which a volatile organic substance 3 is infiltrated into the entire bag is contained and sealed. By doing so, the volatile organic substance 3 can be uniformly and gradually released from the entire surface of the non-porous film 2, that is, the entire container 4. In this case, the sustained release surface of the volatile organic matter occupying the size of the container can be maximized.

  With regard to the thickness of the liquid penetrating member 13, if the thickness is increased, the permeation capacity of the volatile organic substance 3 can be increased, but the thickness of the container is increased. On the contrary, if the thickness of the liquid penetrating member 13 is reduced, the penetration capacity of the volatile organic substance 3 is reduced, but the thickness of the container can be reduced. Therefore, what is necessary is just to adjust the thickness of the liquid permeable member 13 so that the thickness of the container 4 may become desired thickness by these balance. The shape of the liquid penetrating member 13 does not have to be a quadrangle as shown in FIG. 1. For example, the liquid penetrating member 13 is comb-shaped, and non-porous membranes are welded at portions other than the comb teeth. Thus, the entire surface of the liquid permeation member and the non-porous film may be brought into contact with each other by welding and laminating the non-porous films at the holes. In this case, gasification of the volatile organic substance 3 can be suppressed, and the swelling of the container 4 can be prevented. Further, since the liquid penetrating member functions as a core material, there is an effect of improving the strength of the container.

  The non-porous membrane 2 is one that gradually releases molecules of the volatile organic matter 3 by permeation. Examples of the material for the non-porous membrane 2 include polyethylene, polypropylene, polyester, nylon, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, vinylon, and other plastic films, as well as polyethylene, ethylene acrylic acid copolymer, polyethylene terephthalate mixture. Examples of those that can be used include a gas-liquid film such as a system, but it is preferable to use polyethylene or polypropylene that is inexpensive and easily available, and has excellent durability and chemical resistance. Polyethylene and polypropylene have the advantage that they are difficult to permeate water, have appropriate substance permeability and thermoreversibility, are flexible and easy to mold. In addition, it is stable against various substances. Of course, it is not specifically limited to what was mentioned above including polyethylene and a polypropylene. The non-porous membrane 2 can control the amount of molecules of the volatile organic matter 3 to be transmitted by the membrane material, the film thickness, the surface area of the membrane, the molecular weight and properties of the volatile organic matter 3, temperature, external pressure, and the like. It is. According to the inventors' experiments on polyethylene membranes, it has been confirmed that in the case of the same membrane material, the molecular permeation amount varies depending on the film thickness. Therefore, a necessary amount of the volatile organic substance 3 can be supplied at a necessary speed by appropriately selecting a film thickness according to the supply amount of the volatile organic substance necessary for the microorganism. At this time, the volatile organic substance 3 leaks at a moderate rate governed by the permeation performance of the non-porous membrane 2, so that the volatile organic substance 3 is diluted to a concentration that does not affect the survival of microorganisms around the container. Supplied to microorganisms.

Here, the non-porous membrane 2 changes in the molecular permeation amount depending on the density of the membrane. Taking polyethylene as an example, when a low density polyethylene (density of 910 kg / m ³ or more and less than 930 kg / m ³ ) classified by JIS K6922-2 is used, a sufficient amount of volatile organic matter for microorganisms 3 permeates out of the membrane, but when high-density polyethylene (density 942 kg / m ³ or more) is used, the permeation amount of the volatile organic matter 3 out of the membrane decreases. Therefore, what is necessary is just to control the supply amount of the volatile organic substance to microorganisms by the balance of the film thickness and film density of the non-porous membrane 2 according to the desired supply amount of the volatile organic substance. Here, since the film density can be varied by, for example, a stretching process, the film density of a desired film material can be varied by the process, and the supply amount of volatile organic substances can be controlled.

  The permeation of the volatile organic matter 3 through the non-porous membrane 2 occurs when volatile organic matter molecules dissolve in the membrane, and the dissolved molecules diffuse inside the membrane and reach the opposite side. Therefore, catechin, which is a molecule of such a large size that does not dissolve into the film, or a highly polar cyanide compound, does not easily pass through the non-porous film. In addition, since polyethylene, polypropylene, and the like are highly hydrophobic membranes that do not have a functional group compatible with water and have low polarity, water that is a polar molecule hardly dissolves in the membrane. Further, since hydrogen bonds between water molecules are strong, water hardly permeates the membrane at room temperature. Therefore, the non-porous film 2 functions as a “molecular sieve” that transmits a desired volatile organic substance as a main component while hardly transmitting impurities such as water, catechin having a high molecular weight, and a highly polar cyanide. Moreover, the volatile organic substance 3 permeates through the non-porous film 2 in a molecular state, that is, in a gas (gas) state that does not aggregate due to attractive force between molecules like a liquid, and is released gradually. Therefore, the non-porous membrane 2 can also be expressed as a gas permeable membrane.

  In addition, the non-porous membrane is permeated by the volatile organic matter dissolved in the membrane as described above, and the kind and amount of the volatile organic matter is not controlled by the size and number of pores like the porous membrane. Absent. Therefore, there is no problem of hole clogging due to long-term use, and there is no need for regular backwashing. Therefore, it can be used without maintenance for a long time, and the running cost can be reduced.

  Further, the surface property of the non-porous film 2 is preferably determined by the property of the volatile organic material 3 used. For example, if the surface of the non-porous membrane 2 is made hydrophobic, molecules having a hydrophobic group such as a carbon chain can be easily transmitted. On the other hand, if the surface of the non-porous membrane 2 is made hydrophilic, molecules having a hydrophilic group can be easily transmitted. Therefore, what is necessary is just to determine the property of the non-porous membrane 2 surface according to the property of the volatile organic substance 3 to be used. In addition, by imparting polarity to the inside of the membrane, it is possible to strengthen the bonds between the molecular chains constituting the membrane and reduce the gap between the molecular chains, thereby controlling the molecular permeation performance. For example, a film made of polar molecules in which a part of hydrogen of polyethylene is substituted with chlorine, such as polyvinylidene chloride, has a smaller gap between molecular chains and lowers the molecular permeation performance as compared with polyethylene. Furthermore, the permeability | transmittance of a volatile organic substance can also be controlled as a film | membrane which bonds both a hydrophobic film | membrane and a hydrophilic film | membrane and gives both properties.

  Here, the accommodation state of the liquid penetrating member 13 in the container 4 will be described. In the electron donor supply apparatus 1 for microorganisms shown in FIG. 1, the liquid penetrating member 13 is laminated with the non-porous membrane 2, and the liquid penetrating member 13 containing the volatile organic substance 3 and the non-porous member. The membrane 2 is in contact. In this case, the volatile organic substance 3 that is uniformly diffused over the entire surface of the liquid penetrating member 13 can be uniformly and gently supplied from the entire surface of the non-porous membrane 2 to the microorganisms around the container. The thickness can be reduced to about the thickness of the liquid penetrating member 13, and the container 4 becomes very compact. In addition, since the pressing force is applied to the container 4 and the liquid penetrating member is also pressed and crushed, the thickness of the liquid penetrating member 13 may be further reduced. In this way, even when the liquid penetrating member is crushed due to a pressing force, a volatile organic matter permeation path is secured and the volatile organic matter penetrates to every corner of the liquid penetrating member. The area does not decrease.

  In addition, the accommodation state in the container 4 of the liquid permeable member 13 is not limited to the form shown in FIG. For example, as shown in FIG. 2, the liquid permeation is caused by coexisting in the container with a volatile organic substance 3a (hereinafter also referred to as surplus volatile organic substance) in an amount that can be permeated into the liquid permeation member 13. You may accommodate in the state which the non-porous membrane 2 does not contact the whole surface of the member 13. FIG. As shown in FIG. 2, when the container 4 is used in a vertical position, the surplus volatile organic matter 3a accumulates at the bottom of the container. Then, surplus volatile organic substances 3 a accumulated at the bottom of the container 4 are gasified and diffused into the container 4. Therefore, in this case, swelling of the container 4 occurs. However, by applying a pressing force to a part of the container 4 and bringing the non-porous membrane 2 and the liquid penetrating member 13 into contact with each other, the portion to which the pressing force is applied can be made thin. it can. And it becomes possible to store and use a volatile organic substance in the part to which no pressing force is applied. For example, as shown in FIG. 3, since the water pressure is applied when the container lower part 4a is immersed in water, the non-porous membrane 2a of the container lower part 4a below the water surface and the liquid permeable member 13a are brought into contact with each other to be thin, and the surplus Volatile organic substances 3a are pushed up and stored in the container upper part 4b on the water surface where water pressure is not applied. And when the quantity of the volatile organic substance 3 which has osmose | permeated the liquid permeable member 13a of the container lower part 4a reduces, the excess volatile organic substance 3a is osmose | permeated and supplied by the capillary phenomenon through the liquid permeable member 13a. It is possible to continuously release the volatile organic substance 3 from the entire surface of the non-porous film 2a over a long period of time. Here, when it is desired to release the volatile organic substance 3 only from the container lower part 4a to which water pressure is applied, the container upper part 4b is covered with a material that does not transmit volatile organic substances, or the material of the container upper part 4b itself. A material that does not transmit volatile organic substances is used. Note that the container 4 may float even if it is immersed in water. In such a case, a weight (not shown) may be provided at the bottom of the container 4, and the container 4 may be adjusted so as to be immersed to a desired portion depending on the weight of the weight.

  The liquid penetrating member 13 accommodated in the container 4 holds the liquid and functions as a liquid passage. It also serves as a spacer. Therefore, even when a part or the whole of the container 4 is crushed due to a pressing force, the penetration path of the volatile organic matter 3 is secured, and the volatile organic matter 3 penetrates to every corner of the liquid penetration member 13. The sustained release area of the volatile organic substance 3 does not decrease, and even when the container is immersed in water, the volatile organic substance can be uniformly and gradually released from the non-porous film portion of the container. Therefore, not only the case where only the container lower part 4a as shown in FIG. 3 is immersed under the surface of the water, but also the entire container 4 is immersed and used, the volatile organic matter 3 is used for the entire non-porous film portion of the container 4. Can be sustainedly released.

  The electron donor supply device 1 configured as described above is a volatile organic substance that passes through the non-porous membrane 2 as a molecular sieve from inside the container 4 only by being placed near a microorganism that needs to be supplied with the electron donor. Molecules are autonomously and slowly released at a constant rate and supplied to microorganisms. At this time, the amount of the volatile organic substance permeating from the container 4 is controlled to be a required volatile organic substance amount by selecting the material, film thickness, film density, etc. of the non-porous film. It is supplied as a volatile organic substance to a microorganism in a state diluted to a concentration that does not affect the survival of the microorganism. In addition, even if the container is used in an environment where a pressing force is applied, for example, in water, the liquid penetrating member is housed in the container. Securing the liquid penetrating member to keep the volatile organic matter uniformly penetrating the entire surface, and supplying the microorganisms by releasing the volatile organic matter from the entire surface of the non-porous membrane. Is possible.

  Next, FIG. 4 and FIG. 5 show another embodiment. The electron donor supply device for microorganisms of this embodiment does not make the container 4 made of the non-porous membrane 2 completely sealed and independent, but has a means for introducing a volatile organic substance 3. It is a bag-like container that can be replenished with volatile organic substances 3 from the outside.

  The means for introducing the volatile organic substance 3 includes a supply port 5 for injecting the volatile organic substance 3 into a part of the edge of the container 4 as shown in FIG. 4, and a nozzle or pipe 7 as shown in FIG. A structure to be mounted may be used, or a nozzle or pipe 7 integrated with the container 4 may be used. The electron donor supply apparatus 1 for microorganisms shown in FIG. 5 includes a supply nozzle 7 attached to a supply port 5 provided at an edge of the container 4 or a supply nozzle 7 integrated with the container 4 and a volatile organic substance. The tank 6 to be stored is connected by a tube 8 or the like so that the volatile organic substance 3 can be replenished as necessary. In this case, since the tank 6 and the container 4 are communicated with each other through the tube 8, the liquid penetrating member accommodated in the container 4 can be stored by storing the volatile organic substance stock solution 3 ′ in the tank 6. When the volatile organic substance 3 penetrating the liquid 13 decreases, the volatile organic substance 3 ′ can be replenished by the pressure difference between the tank and the container, and supplied to the entire surface of the container 4 through the liquid penetrating member 3. it can. Although the container 4 is provided with the supply port 5 or the nozzle 7, it is not a strict sealing structure. However, in the state where the supply nozzle 7 is filled with the volatile organic substance 3 'supplied from the tank, The liquid level becomes a seal and the inside of the container is practically sealed. For this reason, the volatile organic substance 3 permeating through the liquid penetrating member 13 accommodated in the container 4 does not leak out of the container 4 through the supply port 5 or the nozzle 7.

  Here, in FIG.4 and FIG.5, the accommodation state in the container 4 of the liquid permeable member 13 is a state where the liquid permeable member 13 was laminated by the non-porous film 2 as described above. In this case, the volatile organic substance 3 that is uniformly diffused over the entire surface of the liquid penetrating member 13 can be uniformly and gently supplied from the entire surface of the non-porous membrane 2 to the microorganisms around the container. The thickness can be reduced to about the thickness of the liquid penetrating member 13, and the container 4 becomes very compact.

  The accommodation state of the liquid penetrating member 13 in the container 4 is not limited to the above-described form, and the liquid penetrating member 13 is provided with a gap between the liquid penetrating member 13 and the nonporous membrane 2. May be accommodated. In this case, for example, a part of the container 4 can be made thin by using as follows.

  The electron donor supply apparatus shown in FIG. 6 includes a supply port 5 that can replenish volatile organic substances in the electron donor supply apparatus shown in FIG. In this case, since the volatile organic substance 3 can be replenished to the upper part 4b of the container where no pressing force is applied, the volatile organic substance 3 is replenished arbitrarily or periodically, and the volatile organic substance 3 is stored in the container over a long period of time. 4 can be gradually released.

  Here, since the volume of the container upper portion 4b to which no pressing force is applied increases in proportion to the volume inside the container 4, the volume of the container 4 is increased when it is desired to increase the storage amount of the volatile organic matter 3. Just make it bigger. As described above, when the volatile organic substance 3 is gradually released only from the container lower part 4a to which the pressing force is applied, the permeation of the stored volatile organic substance 3 from the container upper part 4b is prevented. Keep it.

  As described above, by using the electron donor supply device 1 of the present invention as shown in FIG. 6, even if the container is immersed in water in an environment where a pressing force is applied, for example, the lower portion of the container where the pressing force is applied. In 4a, while the penetration path of the volatile organic matter 3 is secured, the container is crushed and thinned by the pressing force, and the volatile organic matter can be stored in the upper portion 4b of the container where no pressing force is applied. This is convenient for supplying the organic material 3. In addition, even if the container is crushed by the pressing force, since the supply path of the volatile organic material 3 is not blocked by accommodating the liquid penetrating member 13, the liquid of the stored volatile organic material 3 While having the advantage that it is easy to supply to the osmotic member 13, the volatile organic substance 3 can be gradually released from the entire surface to which the pressing force is applied.

  As described above, the liquid penetrating member 13 accommodated in the container 4 holds the liquid and functions as a liquid passage. It also serves as a spacer. Therefore, even when the container 4 is crushed due to a pressing force, the penetration path of the volatile organic matter 3 is secured and the volatile organic matter 3 penetrates to every corner of the liquid penetration member 13. Even if the container is immersed in water and used without reducing the sustained release area, the volatile organic substance can be uniformly and gradually released from the non-porous membrane portion of the container. Therefore, it is also possible to use the container 4 by applying a pressing force to the entire portion other than at least the portion of the supply port 5. That is, the entire sustained-release surface other than the supply port 5 of the container 4 may be used by being immersed in water. In this case, although the volatile organic matter cannot be stored in the container 4, the sustained release surface of the volatile organic matter occupying the size of the container can be maximized.

  Further, as shown in FIG. 7, the entire container 4 may be inserted into the sheath body 14 so that the liquid permeable member 13 and the non-porous membrane 2 are brought into contact with each other. In this case, since the sheath body 14 also functions as a protective material that protects the non-porous membrane 2 from external impacts, the container can be made compact and the non-porous membrane can be protected at the same time. The sheath 14 may be anything that does not hinder the sustained release of the volatile organic material 3. For example, although a nonwoven fabric etc. are mentioned, it is not limited to this.

  In addition, only the container lower part 4a is inserted into the sheath body 14, the liquid penetrating member 13a and the nonporous membrane 2a are brought into contact with each other at the inserted part, and the volume of the container upper part 4b not inserted into the sheath body 14 is increased. The volatile organic matter 3 may be stored.

  Here, the container 4 can be processed in advance into the form shown in FIG. For example, as shown in FIG. 8, the container may be divided into an upper part 4b and a lower part 4a, and the upper part 4b and the lower part 4a are connected by a liquid penetrating member 13 so that the volatile organic substance 3 is stored in the upper part 4b. good. More specifically, the boundary portion 15 of the container 4 is welded by heat sealing or the like and partitioned into an upper portion 4b and a lower portion 4a. At this time, a part of the boundary portion 15 is not welded but penetrates the liquid penetrating member 13, the upper portion 4b and the lower portion 4a are communicated with each other by the liquid penetrating member 13, and the volatile organic matter 3 is permeated from the upper portion 4b to the lower portion 4a. The volatile organic substance 3 is supplied by capillary action. With this configuration, the volatile organic substance 3 stored in the upper part 4b of the container 4 permeates the liquid penetrating member 13b penetrating the container upper part 4b and is supplied to the liquid penetrating member 13a of the container lower part 4a. The Then, the volatile organic substance 3 is gradually released from the liquid penetrating member 13a through the nonporous membrane 2a. Here, as shown in FIG. 8, the liquid permeation member 13a of the container lower part 4a is sealed so as to be in contact with the non-porous membrane 2a. That is, by setting the liquid penetrating member 13a to be laminated with the non-porous membrane 2a, it becomes the same form as when put in water.

  In addition, the container upper part 4b shown in FIG. 8 is good also as detachable. For example, when the volatile organic substance 3 stored in the container upper part 4b is exhausted, the boundary part 15 that has been welded is cut to separate the upper part 4b, and the liquid penetrating member 13 exposed from the container lower part 4a. May be inserted into a new container in which the volatile organic substance 3 is sealed, and the container may be bonded to the container lower part 4a and used in a so-called cartridge type.

  Moreover, you may provide a discharge port with the supply port of a volatile organic substance in the container upper part 4b shown in FIG.6 and FIG.8. By providing the discharge port, it is possible to reduce pressure loss when supplying volatile organic substances to the container upper portion 4b. By reducing the pressure loss, unnecessary pressure is not applied to the upper portion 4b of the container, and volatile organic matter does not enter between the liquid permeable member 13a and the non-porous membrane 2a of the lower portion 4a of the container. It permeates into a form suitable for supply of the volatile organic substance 3.

  Next, another embodiment of the electron donor supply device 1 and a manufacturing method thereof will be described. In the case of the bag-like container 4 described above, the container 4 is formed into a bag shape composed entirely of the non-porous film 2, and the periphery is welded by heat sealing or the like, and the sheet shape is infiltrated with the volatile organic matter 3. The liquid penetrating member 13 is sealed. That is, the volatile organic substance 3 is sealed in a container constituted by the non-porous film 2, but in the embodiment described below, a laminated body in which the liquid penetrating member 13 is sandwiched by the non-porous film 2 is formed. In addition, the electron donor supply device 1 is formed by heat-sealing the peripheral edge of the laminate. In addition, the laminated body referred to here is not the liquid permeable member 13 and the non-porous membrane 2 that are bonded or welded on the entire surface or a part thereof, and is simply non-bonded to the liquid permeable member 13 without being bonded or welded. It includes a laminate in which the porous membrane 2 is simply stacked.

  The electron donor supply device of the present invention shown in FIG. 9 is formed by sandwiching the liquid penetrating member 13 between the non-porous membranes 2 to form a laminate, and then heat-sealing the peripheral portion of the laminate. . Here, it is preferable to secure a part of the peripheral part as the volatile organic substance introducing part 20 without heat sealing. In this case, when the volatile organic substance is brought into contact with the volatile organic substance introduction unit 20, the volatile organic substance penetrates and is supplied to the liquid penetrating member 13 by capillary action. For example, the container upper part 4b shown in FIG. 8 described above is connected by attaching a cartridge-type form so as to be detachable, thereby supplying a volatile organic substance. Further, even when the entire periphery is heat-sealed, for example, it is possible to supply a volatile organic substance by inserting a nozzle or the like into a region where the volatile organic substance penetrates. In addition, the non-porous film 2 and the laminated body are formed in a state where the volatile organic material 3 is previously infiltrated into the liquid penetrating member 13, and all the peripheral portions of the laminated body are heat-sealed to penetrate the liquid penetrating member 13. It is also possible to use the volatile organic substance 3 sealed.

  As the liquid permeable member 13 in this case, a material that can be welded to the non-porous membrane and that has a capillary structure closed when heat sealed is used. Accordingly, the volatile organic material 3 is supplied to the entire region surrounded by the capillary structure blocking portion of the heat sealing portion 13 ′ of the liquid penetrating member 13 and the nonporous membrane 2, and the nonporous film 2 other than the peripheral portion is formed. The volatile organic substance 3 can be gradually released from the entire surface.

  Specific examples of the liquid penetrating member 13 used in this case include, for example, a material in which polyethylene or polypropylene is made into a fiber, polyethylene foam, polyurethane foam, vinyl chloride sponge, natural rubber sponge, silicon rubber sponge, or cellulose sponge. . In this case, it is easy to weld with the material of the non-porous film described above, and in particular, when polyethylene or polypropylene is used as the non-porous film, the starting materials of the material are the same or similar and very easy to weld. .

  Here, when the non-porous membrane 2 and the liquid penetrating member 13 are welded, the following method is preferable. The case where a polyethylene fibrous material is used as the liquid permeation member 13 and polyethylene is used as the non-porous membrane 2 will be described as an example. First, the heated and softened polyethylene fibrous material is represented by the non-porous membrane 2. Sow on the surface. Next, another nonporous membrane 2 is placed while the softened state of polyethylene is maintained. Thereby, the liquid permeable member 13 can be welded to the non-porous membrane 2 and held while maintaining the molecular permeability of the polyethylene membrane without heating the polyethylene membrane at a high temperature.

  Here, when the non-porous membrane 2 and the liquid permeable member 13 are welded on the entire surface, there is no gap between the non-porous membrane 2 and the liquid permeable member 3, so that the volatile organic matter that has penetrated by capillary action is a gap. It is preferable because it can be made very thin by preventing bleeding and swelling. However, the non-porous membrane 2 and the liquid penetrating member 13 do not necessarily have to be in contact with each other. For example, the non-porous membrane 2 and the non-porous membrane 13 on the sheet are welded to the entire surface of the sheet without welding the non-porous membrane on the entire surface, and the non-porous membrane 2 and the non-porous membrane 13 are welded only at the peripheral portion to be heat sealed. Capillary occlusion may be performed. Alternatively, the liquid-permeable member 13 and the non-porous membrane 2 are welded or bonded to several places instead of the entire surface, and the non-porous membrane 2 and the liquid-permeable member 13 are welded at the peripheral portion to be heat-sealed. The capillary structure of the osmotic member 13 may be closed.

  Moreover, as shown in FIG. 10, after laminating | stacking the support | carrier 17 which can fix microorganisms on the surface of the non-porous membrane 2, you may heat seal and integrate a peripheral part. As the carrier 17, a polymer gel used for immobilizing microorganisms and enzymes can be used. Specifically, natural polymers such as collagen, fibrin, albumin, casein, cellulose fiber, cellulose triacetate, agar, calcium alginate, carrageenan, agarose, polyacrylamide, poly-2-hydroxyethyl methacrylic acid, polyvinyl chloride, Synthetic polymers such as γ-methylpolyglutamic acid, polystyrene, polyvinylpyrrolidone, polydimethylacrylamide, polyurethane, photocurable resins (polyvinyl alcohol derivatives, polyethylene glycol derivatives, polypropylene glycol derivatives, polybutadiene derivatives, etc.), or composites thereof Can be mentioned.

  Note that a water-absorbing polymer is preferably used as the carrier 17. By using the water-absorbing polymer, the water holding power and water absorbing power of the carrier are enhanced, so that it becomes possible to efficiently remove the target component while supporting the microorganisms in a good state. Here, generally used polymers can be used as the water-absorbing polymer. Specifically, polyacrylic acid, polyaspartic acid, polyglutamic acid, modified products thereof, modified polyethylene glycol, etc. Is mentioned. The modified product referred to here is a product obtained by crosslinking a polymer having an ionic group to a part of the polymer.

  Thus, by providing the carrier 17 on the surface of the non-porous membrane 2 in advance, the microorganism can be fixed to the carrier. Therefore, it is possible to fix the desired microorganisms by immersing the container of the electron donor supply device in the liquid to which the microorganisms are added, or to fix the microorganisms added to the liquid to be treated. It should be noted that the same effect can be obtained even if the electron donor supply apparatus shown in FIGS.

  Further, as shown in FIG. 11, a protective material 16 may be further provided on the surface of the carrier 17. In this case, the electron donor supply device 1 is protected from an external impact and also functions as a reinforcing material. When the weight of the electron donor supply device 1 increases as the size of the electron donor supply device 1 increases, the device is damaged by its own weight. Can be prevented. Even when the protective material 16 is provided alone without the carrier 17, the electron donor supply device 1 can be protected from an external impact and function as a reinforcing material.

  According to the above-described method, it is possible to form a sealed region into which a volatile organic substance permeates by simply heat-sealing the peripheral edge of the laminate, and thus its production is very easy, and electron donor supply to microorganisms. The labor and cost for manufacturing the device can be greatly reduced. Even when the carrier 17 that can carry microorganisms on the surface of the non-porous membrane and the protective material 16 that protects the laminate from external impacts are further provided, the peripheral portion of the laminate is gathered together with the carrier and the protective material. By heat-sealing, a multilayer structure can be easily formed. Therefore, if the multilayer structure is formed to have a large area and a small thickness, a large and thin device can be easily manufactured.

  The method and apparatus 1 for supplying an electron donor to a microorganism described above can be used for any facility that needs to supply an electron donor to a microorganism and for all bioreactors. Further, the environment to be used is not particularly limited, and if the method and apparatus for supplying an electron donor to a microorganism of the present invention is used, volatile organic substances to the microorganism can be gradually and uniformly released even in a liquid. For example, the present invention can be applied to the bioreactor shown in FIGS. In the present embodiment, the case where ammonia oxidizing bacteria and denitrifying bacteria are used as microorganisms will be described. However, the present invention is not limited to this example. In addition to these bacteria, if microorganisms capable of removing a target component are used, ammonia may be used. Components other than nitrogen compounds such as nitrate ions and nitrite ions can be removed. The bioreactor 9 of the embodiment shown in FIG. 12 and FIG. 13 (A) includes a carrier 11 supporting ammonia oxidizing bacteria and denitrifying bacteria, a bag 10 made of a nonwoven fabric for structural reinforcement of the carrier 11, and the nonwoven fabric. Volatile organic matter that functions as an electron donor serving as an energy source for denitrifying bacteria housed in a pocket 12 formed inside a bag-like carrier 11 reinforced by the bag 10 and being fixed to the carrier 11 autonomously. And a container 4 in which the electron donor supply device 1 that supplies the powder slowly at a constant speed is sealed. The carrier 11 is applied to the inner surface or the front surface of the non-woven bag 10 and is provided so as to maintain a certain form with the non-woven bag 10 as a reinforcing structure. The material for reinforcing the carrier is not limited to a nonwoven fabric, and a nylon net or the like may be used.

  As the carrier 11, a polymer gel used for immobilizing microorganisms and enzymes can be used. Specifically, natural polymers such as collagen, fibrin, albumin, casein, cellulose fiber, cellulose triacetate, agar, calcium alginate, carrageenan, agarose, polyacrylamide, poly-2-hydroxyethyl methacrylic acid, polyvinyl chloride, Synthetic polymers such as γ-methylpolyglutamic acid, polystyrene, polyvinylpyrrolidone, polydimethylacrylamide, polyurethane, photocurable resins (polyvinyl alcohol derivatives, polyethylene glycol derivatives, polypropylene glycol derivatives, polybutadiene derivatives, etc.), or composites thereof Can be mentioned.

  Note that a water-absorbing polymer is preferably used as the carrier 11. By using the water-absorbing polymer, the water holding power and water absorbing power of the carrier are enhanced, so that it becomes possible to efficiently remove the target component while supporting the microorganisms in a good state. Here, generally used polymers can be used as the water-absorbing polymer. Specifically, polyacrylic acid, polyaspartic acid, polyglutamic acid, modified products thereof, modified polyethylene glycol, etc. Is mentioned. The modified product referred to here is a product obtained by crosslinking a polymer having an ionic group to a part of the polymer.

  In addition, the carrier 11 is not limited to the above-described one, and the nonwoven fabric may be brushed and the microorganisms may be directly supported thereon, or the surface of the non-porous membrane 2 may be brushed, You may make it carry | support a microorganism.

In addition, ammonia-oxidizing bacteria and denitrifying bacteria can be conventionally known in this type of field, more specifically, for example, as ammonia-oxidizing bacteria,
Nitrosomonas europaea IFO-14298,
Nitrosomonas europaea, N.marina ^* ,
Nitrosococcus oceanus ^* , N.mobilis,
Nitrosospira briensis,
Nitroso lobus multiformis,
Nitrosovibrio tenuis,
As denitrifying bacteria,
Paracoccus denitrificans JCM-6892,
Paracoccus denitrificans,
Alcaligenes eutrophus, A. faecalis,
Alcaligenes sp. Ab-A-1, Ab-A-2, GA-2-1 (FERM P-13862, P-13860, P-13861) ^*
Pseudomonas denitrificans,
And so on.

In addition, you may further carry | support nitrite oxidation bacteria. As the nitrite oxidizing bacteria, those conventionally known in this type of field can be used. More specifically, for example,
Nitrobacter winogradskyi N. hamburgensis
Nitrospina gracilis ^*
Nitrococcus mobilis ^*
Nitrospira marina ^*
And so on.

  Note that the strains marked with * in the above are strains that can be applied only to seawater treatment, and the other strains can be applied only to freshwater treatment. N.europaea and N.winogradskyi can be used both in fresh water and in sea water. The strain to which the deposit number is attached is a strain deposited by the applicant.

  Ammonia-oxidizing bacteria are aerobic microorganisms that convert (oxidize) ammonia (ammonium ions) into nitrite ions, and denitrifying bacteria are anaerobic microorganisms that convert (reducing) nitrate ions and nitrite ions to nitrogen gas. In other words, if a bioreactor carrying ammonia-oxidizing bacteria is used under aerobic conditions, it is possible to convert the ammonia into nitrite ions and suppress malodor. If a bioreactor carrying denitrifying bacteria is used under anaerobic conditions, nitrate ions and nitrite ions are converted into harmless nitrogen gas. By using these bacteria in combination, ammonia, nitrate ions, and nitrite ions can be removed. When oxygen is supplied to ammonia-oxidizing bacteria, the function of denitrifying bacteria, which are anaerobic microorganisms, is reduced. In this case, denitrifying bacteria are supplied in a suitable region in the bioreactor, that is, oxygen is supplied. Denitrification is locally distributed in an anaerobic region away from the location. Nitrite-oxidizing bacteria are microorganisms that oxidize nitrite ions to nitrate ions. By supporting these bacteria, denitrification reaction occurs more efficiently.

  The above strains may be fixed to the carrier alone, or may be fixed in combination with the same or different strains.

  According to the bioreactor configured as described above, the volatile organic substance 3 permeating the liquid permeable member 13 accommodated in the container 4 permeates the non-porous membrane 2 and surrounds the container 4, that is, the container 4. Leaks into the bag (pocket 12) of the outer carrier 11 that further covers the surface of the carrier 11 and diffuses within the bag of the carrier 11 to uniformly supply the microorganisms that require the electron donor, that is, denitrifying bacteria, to the fixed surface. That is, it becomes possible to supply the volatile organic substance 3 functioning as an electron donor serving as an energy source to the microorganisms to the microorganisms fixed to the carrier autonomously with uniform and gentle sustained release. This bioreactor is configured by simply inserting a container 4 as an electron donor supply device in which a liquid permeation member 13 in which a volatile organic substance 3 is permeated into a bag 10 of a carrier 11 is sealed. When the volatile organic matter 3 penetrating the liquid penetrating member 13 is used up, the volatile organic matter 3 penetrating the liquid penetrating member 13 is replaced with a new sealed bag so that it is continuously in the liquid to be treated. The ammonia, nitrate ions, and nitrite ions can be changed to nitrogen and removed. In addition, even if the liquid to be treated is filled around the container 4, the denitrifying bacteria function, and by aeration of the front side surface of the bioreactor, the ammonia oxidizing bacteria are activated and ammonia can be efficiently removed. It becomes like this.

  Further, as shown in FIG. 13B, instead of the container 4 as the electron donor supply device of the bioreactor 9 of the embodiment shown in FIG. 12, there is means for introducing the volatile organic substance 3 shown in FIG. It is also possible to use an electron donor supply device that is a sealed bag-like container and that can replenish the volatile organic substance 3 shown in FIG. 5 from the outside. In this case, if the volatile organic substance stock solution 3 ′ is stored in the tank 6, when the volatile organic substance 3 penetrating the liquid penetrating member 13 in the container 4 decreases, Since the volatile organic substance 3 'is replenished by the pressure difference between the tank and the container, the target compound in the liquid to be treated can be removed for a long time or a long time regardless of the size of the container / bag 4, such as ammonia removal. Can be implemented. In addition, in this case, if the amount of volatile organic substances 3 ′ in the tank 6 is monitored and replenished appropriately, it is not necessary to individually control and monitor a large number of electron donor supply devices connected to the tank 6. .

  Here, as described above, the electron donor supply device 1 of the present invention can make the container lower part 4a thinner by immersing the container lower part 4a in water as shown in FIG. Therefore, as shown in FIG. 14, when the container lower portion 4 a of the electron donor supply device 1 is put in the bag-like bioreactor 9 and immersed in water, the bioreactor bag and the electron donor supply device 1 container lower portion Water pressure is applied to 4a, and the thickness of the bioreactor can be reduced. Accordingly, even if a plurality of bioreactors are provided in the water, the bioreactors are not bulky, so that a plurality of bioreactors can be provided in an integrated manner. A portion other than the supply port 5 of the container 4 may be placed in a bioreactor and immersed in water to widen the sustained release surface.

  Moreover, you may comprise the bioreactor which integrated the support | carrier 11 which fixed the container 4 of the above-mentioned electron donor supply apparatus, and the microorganisms effective for the removal of the target component. For example, the part of the non-porous film 2 of the container 4 that seals the volatile organic substance 3 is attached so as to contact the carrier 11, thereby configuring a bioreactor in which the carrier 11 and the electron donor supply device 1 are integrated. To do. In this case, since the microorganism is fixed on the surface through which the volatile organic substance 3 permeates, the entire amount of the supplied volatile organic substance is directly supplied to the microorganism. Also in this case, when the bioreactor is immersed in water, its thickness becomes thin and it is easy to accumulate. Therefore, it is possible to increase the density when the bioreactor is accommodated in a processing tank or the like.

  The bioreactor may be a sheath body. In other words, the bag of the carrier 11 is made tight, the container lower part 4a of the electron donor supply device 1 to be put in is thinly crushed, and the volatile organic substance 3 is transferred from the container upper part 4b outside the bag of the carrier 11 to the liquid penetrating member 13. The volatile organic substance 3 may be gradually released from the entire surface of the container lower part 4a. By doing so, the bioreactor can be made thin and compact, the bioreactor functioning as a sheath functions as a protective material, and the electron donor supply device 1 is protected from external impact such as friction. .

  Next, an embodiment of the gaseous ammonia removing apparatus of the present invention shown in FIG. 17 will be described. The gaseous ammonia removing apparatus 20 of the present invention includes a gas introducing unit 27 for introducing gaseous ammonia, a watering means for obtaining water containing ammonia by bringing water into contact with the gaseous ammonia introduced from the gas introducing unit 27, a gas And a microbial treatment region 28 for decomposing ammonium ions contained in the water by bringing the water in contact with the gaseous ammonia into contact therewith, and the microbial treatment region 28 further comprises ammonia oxidizing bacteria or ammonia oxidizing bacteria and nitrite oxidation. In addition to the presence of bacteria and denitrifying bacteria, the electron donor supply device 1 of the present invention is arranged. The watering means includes a watering pump 21 that pumps up the water 25 stored in the circulation tank 24, a pipe 22 that allows the water pumped up by the watering pump 21 to pass therethrough, and a watering pipe 23 that sprays the water 25 downward. The

  Gaseous ammonia is introduced into the gaseous ammonia removal device 20 from the gas introduction unit 27. In the present embodiment, the gas introduction part 27 is provided immediately below the watering nozzle 23. However, since gaseous ammonia is lighter than air, the gas introduction part 27 is provided under the microorganism treatment region 28 to provide gaseous ammonia. May be diffused upward in the apparatus 20. Next, the water 25 in the circulation tank 24 is pumped up by the watering pump 21, passes through the pipe 22, and is sprinkled from the watering pipe 23. The sprinkled water 25 comes into contact with and dissolves gaseous ammonia introduced into the apparatus 20, converts the gaseous ammonia into ammonium ions, and comes into contact with the microorganism treatment region 28. Ammonium ions contained in the water 25 are oxidized to nitrite ions by ammonia oxidizing bacteria, and are also oxidized to nitrate ions when nitrite oxidizing bacteria are also present. And the nitrite ion produced | generated by ammonia oxidizing bacteria, the nitrite ion produced | generated by ammonia oxidizing bacteria, and the nitrate ion produced | generated by the nitrite oxidizing bacteria are reduced to nitrogen gas by denitrifying bacteria. Therefore, the gaseous ammonia removing device 20 can deodorize and detoxify the gaseous ammonia. Further, when the water 25 and the microorganism treatment area 28 come into contact with each other, water is simultaneously supplied to the microorganisms existing in the microorganism treatment area. The water 25 that has passed through the microorganism treatment region 28 returns to the circulation tank 24. At this time, ammonium ions that have not been removed may enter the circulation tank 24 and raise the pH. Therefore, a water supply means 26 is provided to dilute the water 25 in the circulation tank 24 to keep the pH constant. I try to keep the value.

  Here, there is no particular limitation on the method of causing ammonia oxidizing bacteria or ammonia oxidizing bacteria and nitrite oxidizing bacteria and denitrifying bacteria to exist in the microorganism treatment region 28. For example, they may be supported on the carrier 17 described above, or porous. A body or the like may be used. The arrangement of the electron donor supply device 1 is not particularly limited as long as the volatile organic substance 3 can be supplied to the denitrifying bacteria. Note that the bioreactor 9 of the present invention may be arranged in place of the microorganism treatment region 28. The manner of arrangement of the bioreactors 9 is not particularly limited, but it is preferable to arrange a plurality of bioreactors 9 so as to face each other and arrange the bioreactors 9 so that the surface of the bioreactors 9 and the water spray direction are parallel. In this case, the integration density of the bioreactor 9 can be improved, and water can easily pass through each bioreactor, so that the removal efficiency of gaseous ammonia is improved.

  The above-described embodiment is an example of a preferred embodiment of the present invention, but is not limited thereto, and various modifications can be made without departing from the scope of the present invention.

Example 1
The effectiveness of the electron donor supply device of the present invention was confirmed by measuring the amount of organic matter permeated when a bag was formed using a polyethylene film and methanol and ethanol were sealed therein.
Methanol (made by Wako Pure Chemical Industries, 99.8%) in a polyethylene film (trade name: Mipolon film, manufactured by Mitsuwa Corp.) having a thickness of 0.05 mm, 0.1 mm, 0.3 mm, 0.5 mm, Ethanol (made by Wako Pure Chemical Industries, 99.5%) was sealed to form a bag, immersed in water, and measured for TOC concentration with respect to the number of days passed. Permeation of methanol and ethanol Evaluated. The TOC concentration was measured by a combustion-infrared total organic carbon analyzer (TOC-650, manufactured by Toray Engineering). The results are shown in FIGS. 15A and 15B. In the figure, B represents background, MeOH represents methanol, EtOH represents ethanol, and numerical values such as 0.05, 0.1, 0.3, and 0.5 represent polyethylene film thickness (unit: mm). From this experiment, it was confirmed that the supply amount of the electron donor can be controlled by the thickness of the polyethylene film because the TOC concentration increases as the thickness of the polyethylene film decreases in both methanol and ethanol. . Therefore, by using this principle, a volatile organic substance such as methanol or ethanol is permeated into a liquid penetrating member such as filter paper, and then sealed in a nonporous membrane such as a polyethylene membrane, thereby using a nonporous membrane. Can be gradually and gradually released from the entire surface.

(Example 2)
The function of the bioreactor was confirmed using the polyethylene bag for sealing ethanol used in Example 1.

(Test strain and its culture)
Nitrosomonas europaea IFO-14298 was used as an ammonia oxidizing bacterium, and Paracoccus denitrificans JCM-6892 was used as a denitrifying bacterium. For the culture, a liquid medium based on IFO Medium List No. 240 for Nitrosomonas europaea and JCM Medium List No. 22 (Nutrient agar No. 2) for Paracoccus denitrificans was used. The composition of the medium is shown in Table 1. Phenol Red was added as a pH indicator to IFO medium No. 240, and the pH was adjusted by appropriately adding Na ₂ CO ₃ instead of CaCO ₃ . In addition, JCM medium No. Agar was removed from No. 22 and used as a liquid medium. After culturing at 30 ° C. (110 rpm), the cells were collected by centrifugation, and phosphate buffer (9 g / l Na ₂ HPO ₄ · 12H ₂ O, 1.5 g / l KH ₂ PO ₄ , pH = 7. Washed 3 times according to 5). As for the washed cells, N. europaea was 8 mg dry wt. / Ml, P. denitrificans was 33 mg dry wt. / Ml each was suspended in a phosphate buffer.

(Method for immobilizing bacteria)
Immobilization by mixing 1 ml of the above-mentioned N. europaea fungus suspension and 2 ml of the P. denitrificans fungus suspension with 9 ml of the photocurable resin PVA-SbQ (SPP-H-13, manufactured by Toyo Gosei Co., Ltd.) did. The mixed solution of the bacterial cells and the resin was directly applied to the nonwoven fabric and irradiated for 1 hour under a metal halogen lamp to form an immobilization carrier (length 50 mm, width 50 mm, thickness 20 mm) in a sheet form on one side of the nonwoven fabric.

(Performance evaluation)
The performance of the bioreactor using an immobilization carrier when using an electron donor supply device in which ethanol was sealed with a polyethylene membrane was evaluated.
The carrier prepared by embedding Nitrosomonas europaea IFO-14298 and Paracoccus denitrificans JCM-6892 formed in the above-mentioned example is formed into a sheet on one side of the nonwoven fabric so that the nonwoven fabric is on the outside and the carrier is an electron A pocket for the donor supply control device is provided, and a bag-like electron donor supply control device in which ethanol is sealed with a polyethylene film having a thickness of 0.05 mm and 0.3 mm is put therein, and the ammonia drainage treatment is performed. The ability was evaluated.

(Analysis method)
The ammonia and nitrous acid concentrations in the medium solution were measured by indophenol blue absorptiometry and naphthylamine absorptiometry, respectively.

(Performance evaluation results when using an electron donor supply device in which ethanol is sealed with a polyethylene membrane in a bioreactor using an immobilized carrier)
FIG. 16 shows the results of performance evaluation of the bioreactor. C is a bioreactor not supplied with an electron donor, EtOH-0.05 is a bioreactor using an electron donor supply device in which ethanol is sealed with a polyethylene film thickness of 0.05 mm, and EtOH-0.3 is a polyethylene film. It is the result of the bioreactor using the electron donor supply apparatus which sealed ethanol with thickness 0.3mm. In C, EtOH-0.05, and EtOH-0.3, the ammonia concentration became 0 on the 4th day, but the nitrite concentration continued to rise until the 7th day in the case of C. EtOH-0 .3 increased until the 2nd day, but decreased thereafter and was not detected on the 7th day, and EtOH-0.05 did not detect nitrite from the 1st day. Therefore, it was confirmed that ethanol was supplied to the bioreactor via the polyethylene membrane, and it was confirmed that the thinner the polyethylene film thickness, the easier to supply ethanol. From the above results, even when a volatile organic substance such as ethanol is infiltrated into a liquid permeable member and then sealed with a polyethylene film or the like as in the present invention, the volatile organic substance is used as an electron donor for the microorganism (denitrifying bacteria). It is possible to convert ammonia and nitrite ions into harmless nitrogen gas.

It is a figure which shows the example of the sealing type (laminate) which is one Embodiment of the electron donor supply apparatus of this invention, (A) is a perspective view, (B) is a longitudinal cross-sectional view. It is a longitudinal cross-sectional view which shows the other sealing form which is one Embodiment of the electron donor supply apparatus of this invention. It is a longitudinal cross-sectional view which shows the form at the time of using the lower part of the electron donor supply apparatus of this invention shown in FIG. 2 immersed in water. It is a longitudinal cross-sectional view which shows the example of the replenishment type which is other embodiment of the electron donor supply control apparatus of this invention. It is the schematic which shows the whole structure of the electron donor supply control apparatus of embodiment of FIG. It is a longitudinal cross-sectional view which shows the form at the time of using the lower part of the electron donor supply apparatus of this invention shown in FIG. 2 immersed in water. It is a longitudinal cross-sectional view which shows the form at the time of using the container lower part of the electron donor supply apparatus of this invention shown in FIG. It is a perspective view which shows the form at the time of processing the electron donor supply apparatus of this invention previously. It is a figure which shows the electron donor supply apparatus at the time of forming by heat-sealing a peripheral part, after forming a laminated body by pinching | interposing a liquid permeable member with a non-porous film, (A) is a perspective view, (B) is It is a longitudinal cross-sectional view. It is a figure which shows the example which equipped the support | carrier on the surface of the nonporous film | membrane of the electron donor supply apparatus of this invention shown in FIG. It is a figure which shows the example which equipped the support | carrier and the protective material on the surface of the non-porous film | membrane of the electron donor supply apparatus of this invention shown in FIG. It is a perspective view which shows an example of a structure of the bioreactor using the electron donor supply apparatus of this invention. It is a longitudinal cross-sectional view which shows an example of a structure of the bioreactor of this invention, (A) shows the example of a sealing type, (B) shows the example of a replenishment type, respectively. It is a longitudinal cross-sectional view which shows the form at the time of using the bioreactor of this invention in water. It is a figure which shows the permeation | transmission amount measurement result of the volatile organic substance from a polyethylene film, (A) shows methanol and (B) shows each measurement result of ethanol. It is a figure which shows the performance evaluation result when using the electron donor supply apparatus which sealed ethanol with the polyethylene membrane for the bioreactor using the fixed support | carrier, (A) is the relationship between ammonia concentration and elapsed days, (B ) Shows the relationship between the nitrite concentration and the number of days elapsed. It is the schematic which shows an example of a structure of the gaseous ammonia removal apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electron donor supply apparatus 2 Non-porous membrane 3 Volatile organic substance 4 Container 4a Container lower part 4b Container upper part 5 Supply port 6 Volatile organic substance storage tank 7 Supply nozzle 8 Tube 9 Bioreactor 10 Nonwoven fabric 11 Carrier 12 Electron donor supply apparatus Pocket 13 Liquid penetrating member 14 Sheath body 16 Protective material 17 Carrier 20 Gaseous ammonia removal device 21 Sprinkling pump 25 Water 27 Gas inlet 28 Microbial treatment region

Claims (30)

  A volatile organic substance that functions as an electron donor serving as an energy source for microorganisms, a liquid penetrating member that can infiltrate the volatile organic substance, and a container having a sealed structure including at least a non-porous film, The liquid penetrating member is housed in a container together with the volatile organic substance, and the liquid penetrating member permeates the volatile organic substance by capillary action and supplies it to every corner of the surface in contact with the non-porous film. An electron donor to a microorganism that supplies the volatile organic substance from the non-porous membrane portion of the container to a microorganism around the container at a speed governed by the molecular permeation performance of the non-porous film. Feeding device.   Liquid penetrating member capable of penetrating a volatile organic substance functioning as an electron donor serving as an energy source for microorganisms, a container having a non-porous membrane partially sealed, and the volatile organic substance provided in the container The liquid penetrating member is accommodated in the container, and the liquid penetrating member permeates the volatile organic matter by capillary action and is in contact with the non-porous membrane. The volatile organic matter is replenished from the supply port to allow the volatile organic matter to permeate the liquid penetrating member, and the volatile organic matter is introduced from the non-porous membrane portion of the container. An apparatus for supplying an electron donor to a microorganism, which supplies the microorganism around the container at a speed governed by the molecular permeation performance of the non-porous membrane.   The apparatus for supplying an electron donor to a microorganism according to claim 2, wherein the supply port is equipped with a supply nozzle that communicates with a volatile organic substance storage tank and can replenish the volatile organic substance as necessary.   The container is divided into two regions, and the liquid penetrating member is disposed across the two regions to communicate the two regions, and the volatile organic matter is stored in one of the two regions. The electron donor supply device to the microorganism according to any one of claims 1 to 3.   The apparatus for supplying an electron donor to a microorganism according to any one of claims 1 to 3, wherein the container has a bag shape.   A liquid penetrating member capable of penetrating a volatile organic substance functioning as an electron donor serving as an energy source for microorganisms, and a non-porous film, the liquid penetrating member penetrating the volatile organic substance by capillary action, and Supplying to every corner of the surface in contact with the non-porous membrane, and a laminate in which the liquid penetrating member is sandwiched by the non-porous membrane is formed, and a peripheral portion of the laminate A device for supplying an electron donor to a microorganism in which the capillary structure of the liquid penetrating member is closed by heat sealing.   The laminated body is heat-sealed except for a part thereof to close the capillary structure of the liquid-permeable member, and a part of the peripheral part is volatile without blocking the capillary structure of the liquid-permeable member. The apparatus for supplying an electron donor to a microorganism according to claim 6, which is secured as an introduction part of an organic substance.   The apparatus for supplying an electron donor to a microorganism according to any one of claims 1 to 7, wherein the volatile organic substance is waste alcohol.   The apparatus for supplying an electron donor to a microorganism according to any one of claims 1 to 8, wherein the non-porous film is a polyethylene film or a polypropylene film.   The apparatus for supplying an electron donor to a microorganism according to any one of claims 1 to 9, wherein a protective material for protecting the non-porous film is provided on a surface of the non-porous film.   The apparatus for supplying an electron donor to a microorganism according to any one of claims 1 to 9, wherein a carrier capable of supporting the microorganism is provided on a surface of the non-porous membrane.   The surface of the non-porous membrane is provided with a carrier capable of supporting microorganisms, and the surface of the carrier is provided with a protective material for protecting the non-porous membrane. The electron donor supply device to the microorganism according to Item.   The apparatus for supplying an electron donor to a microorganism according to claim 11 or 12, wherein the carrier is a water-absorbing polymer.   A step of sandwiching a liquid permeation member capable of permeating volatile organic substances with a non-porous film to form a laminate, and a step of heat-sealing the peripheral portion of the laminate to close the capillary structure of the liquid permeation member; And the liquid penetrating member permeates the volatile organic substance by capillary action and supplies it to every corner of the surface in contact with the non-porous membrane. .   One of a step of forming a laminate by sandwiching a liquid permeation member capable of permeating volatile organic substances with a non-porous membrane, a carrier capable of supporting microorganisms, and a protective material protecting the laminate from external impacts or A step of providing both on the surface of the laminate, and a step of heat-sealing a peripheral portion of the laminate to close the capillary structure of the liquid-permeable member, and the liquid-permeable member capillaries the volatile organic matter. A method for producing an electron donor supply device for microorganisms, which is supplied to every corner of the surface in contact with the non-porous membrane by being permeated by the method.   In the step of heat-sealing the peripheral portion of the laminated body to close the capillary structure of the liquid-permeable member, the capillary structure of the liquid-permeable member is closed by heat-sealing except for the peripheral portion of the laminated body. The method for producing an electron donor supply device for a microorganism according to claim 14 or 15, wherein a part of the peripheral portion is secured as an introduction portion for the volatile organic matter without blocking the capillary structure of the liquid penetrating member.   A liquid-permeable member capable of permeating the volatile organic substance together with the volatile organic substance functioning as an electron donor serving as an energy source of microorganisms is contained in a container having a sealed structure including at least a part of the non-porous film, and the liquid The osmotic member penetrates the volatile organic substance by capillary action and supplies it to every corner of the surface in contact with the non-porous membrane, and the volatile organic substance penetrates the entire surface of the liquid permeable member. To the corners of the surface of the non-porous membrane that is in contact with the liquid penetrating member, the volatile organic matter is transferred from the non-porous membrane portion of the container to the molecular permeation performance of the non-porous membrane. A method for supplying an electron donor to a microorganism, wherein the microorganism is supplied to the microorganism around the container at a controlled rate.   A container having a sealed structure including at least a part of a non-porous membrane contains a liquid penetrating member capable of penetrating a volatile organic substance functioning as an electron donor serving as an energy source of microorganisms and supplemented with the volatile organic substance. A supply port to be obtained is provided in the container, and the volatile organic matter is permeated into the liquid penetrating member by replenishing the volatile organic matter from the supply port, and the liquid penetrating member penetrates the volatile organic matter by capillary action. And supplying to every corner of the surface that is in contact with the non-porous membrane, and the non-volatile organic matter that has permeated the entire surface of the liquid permeable member is in contact with the liquid permeable member. Microorganisms around the container are supplied to every corner of the surface of the porous membrane, and the volatile organic substance is controlled from the nonporous membrane portion of the container to the molecular permeation performance of the nonporous membrane. Electron donor supply method to the microorganisms and supplying.   The volatile organic substance is stored in an upper portion of the container that is not subjected to the pressing force while applying a pressing force to the lower portion of the container, and the liquid penetrating member is disposed across the lower portion and the upper portion of the container. The method for supplying an electron donor to a microorganism according to claim 17 or 18, wherein the stored volatile organic substance is supplied by penetrating the entire surface of the liquid penetrating member.   The support | carrier which fixed the microorganisms effective in the removal of the target component is arrange | positioned around the non-porous membrane part of the electron donor supply apparatus to the microorganisms of any one of Claims 1-10. Bioreactor.   21. The bioreactor according to claim 20, wherein the carrier is applied to and adhered to the non-porous membrane part.   The bioreactor according to claim 20, wherein the carrier is formed into a bag shape, and the electron donor supply device for microorganisms according to any one of claims 1 to 10 is accommodated in a space inside the bag.   21. A bioreactor according to claim 20, wherein the carrier is a water-absorbing polymer.   The bioreactor which makes microorganisms carry | support directly on the surface of the said non-porous membrane of the electron donor supply apparatus to microorganisms of any one of Claims 1-10.   A liquid to be treated is provided on one surface of a carrier on which one or two or more microorganisms that are effective in removing a target component in the liquid to be treated and microorganisms that oxidize or reduce substances produced by the microorganism are immobilized. 21. The bioreactor according to claim 20, wherein the electron donor supply device for microorganisms according to any one of claims 1 to 10 is brought into contact with the other surface.   The bioreactor according to claim 25, wherein ammonia-oxidizing bacteria are used as microorganisms effective for removing a target component in the liquid to be treated, and denitrifying bacteria are used as microorganisms that reduce substances produced by the microorganisms.   A first step of bringing gaseous ammonia and water into contact with each other to dissolve the gaseous ammonia in the water; and the water that has been brought into contact with the gaseous ammonia to be ammonia oxidizing bacteria or ammonia oxidizing bacteria and nitrite oxidizing bacteria; A second step of contacting a microbial region where denitrifying bacteria are present, and arranging the electron donor supply device according to any one of claims 1 to 10 in the microbial region, and Organic matter is supplied from the non-porous membrane portion of the container of the electron donor supply device to the denitrifying bacteria around the container at a rate governed by the molecular permeation performance of the non-porous membrane, and generated by the ammonia oxidizing bacteria Nitrite ions produced by the ammonia-oxidizing bacteria and gaseous ammonia that is reduced to nitrogen gas by the nitrate ions produced by the nitrite-oxidizing bacteria Method. Contacting the gaseous ammonia and water, a first step of obtaining a ammonia-containing water to dissolve the gaseous ammonia to the water, the second contacting the ammonia-containing water to the bioreactor of claim 26 The gaseous ammonia removal method including these steps.   A gas introduction part for introducing gaseous ammonia; watering means for obtaining ammonia-containing water by bringing water into contact with the gaseous ammonia introduced from the gas introduction part; and the ammonia-containing water by bringing the ammonia-containing water into contact therewith. A microbial treatment region for decomposing ammonium ions contained in the microbial treatment region, wherein the microbial treatment region contains ammonia-oxidizing bacteria or ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, and denitrifying bacteria, and An apparatus for removing gaseous ammonia, comprising the electron donor supply device according to claim 1.   A gas introduction part for introducing gaseous ammonia; watering means for obtaining ammonia-containing water by bringing water into contact with the gaseous ammonia introduced from the gas introduction part; and the ammonia-containing water by bringing the ammonia-containing water into contact therewith. An apparatus for removing gaseous ammonia, comprising the bioreactor according to claim 26, wherein the bioreactor according to claim 26 decomposes ammonium ions contained in the gas.

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